JPS6039660B2 - Method for producing 3,3',5,5'-tetrahydroxymethyl-4,4'-dihydroxydiphenylmethanes - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides 3,3,5,5-tetrahydroxymethyl-4,4-
The present invention relates to a method for producing dihydroxydiphenylmethanes in high yield.

3.3.5.5-Tetrahydroxymethyl-4.4-dihydroxydiphenylmethane is a compound used as a polymerization raw material for phenol resins, epoxy resins, polyester resins, and the like.

Subordinates: 3.3.5 from phenols and formaldehyde
・Methods for synthesizing 5'-tetrahydroxymethyl-4,4'-dihydroxydiphenylmethanes, such as 3,3,5,5-tetrahydroxymethyl-4,4'-dihydroxydiphenylmethane, have been reported in many literatures. has been done.

However, in both of these methods, phenols and formaldehyde are reacted in the presence of a basic compound containing an alkali metal or an alkali metal.
The yield of 3,3,5,5-tetrahydroxymethyl-4,4'-dihydroxydiphenylmethane is low due to the large amount of by-products of high-boiling compounds, and this method cannot be satisfactorily adopted as an industrial production method. The present inventors have found that when a basic compound containing an alkali metal or alkali metal is reacted in the coexistence of an alkali metal salt or an alkali metal salt, 313.5.5-tetrahydroxymethyl-4.4 -Dihydroxyphenylmethanes can be obtained in high yield, and the present invention has been achieved.

That is, the present invention provides at least one basic compound ta' selected from the group consisting of basic compounds containing alkal metals or alkali metals, and at least one basic compound ta' selected from the group consisting of alkali metal salts and alkali metal salts. 3, characterized in that a phenol selected from the group consisting of phenol and pis(4-hydroxyphenyl)methane is reacted with formaldehyde in the coexistence of at least one metal salt 'b' of -3,5,5-tetrahydride. This is a method for producing oxymethyl-4,4'-dihydroxydiphenylmethane. The phenols used as raw materials in the method of the present invention are phenols selected from the group consisting of phenol and bis(4-hydroxyphenyl)methanes, and specifically phenolbis(4-hydroxyphenyl)methanes. ) methane, and bis(4-hydroxyphenyl)methanes such as 2,2-bis(4-hydroxyphenyl)propane.

Among these phenols, it is preferable to use monohydric phenols, and it is particularly preferable to apply the method of the present invention to phenol. In addition to formaldehyde, the formaldehyde used in the method of the present invention for reacting phenols with formaldehyde may include formalin, which is an aqueous solution thereof, or a polymer of formaldehyde, which can easily produce formaldehyde. Paraformaldehyde can be exemplified. Among these, formalin is preferably used in the method of the present invention. The amount of formaldehyde used is usually 0.5 to 5, preferably 2 to 3.5 in molar ratio to the phenols.
is within the range of The basic compound used in the method of the present invention is a basic compound containing an alkali metal or an alkali metal. More specifically, lithium hydroxide, sodium hydroxide, potassium hydroxide, lithium oxide, sodium oxide, potassium oxide, lithium methoxide, lithium ethoxide, lithium propoxide, lithium butoxide, sodium methoxide, sodium ethoxide, Basic compounds containing alkali metals such as sodium bopoxide, sodium butoxide, potassium methoxide, potassium ethoxide, potassium propoxide, potassium butoxide, magnesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide, oxidized Examples include basic compounds containing alkali metals such as magnesium, calcium oxide, strontium oxide, barium oxide, magnesium methoxide, calcium methoxide, strontium methoxide, and barium methoxide. At least one basic compound among these basic compounds is used,
It can also be used as a mixture of two or more types. Among these basic compounds, it is preferable to use a basic compound containing an alkali IJ metal,
Particular preference is given to using basic compounds containing sodium. Among them, it is particularly preferable to use sodium hydroxide in the method of the present invention. In the method of the present invention, when the phenols are reacted in the presence of the alkali metal or alkali metal-containing basic compound, the phenols are converted into alkali metal salts or alkali metal salts. In place of the above-mentioned phenols and basic compounds, alkali metal salts or alkali metal salts of phenols can also be used, which naturally also falls within the scope of the present invention. The metal salt used in the method of the present invention is at least one metal salt selected from the group consisting of alkali metal salts and alkali metal salts. For example, specifically, lithium,
Halogen compounds such as fluorides, chlorides, bromides, iodides, etc. of alkali metals such as sodium and potassium, nitrates,
Inorganic acid salts such as sulfates, perchlorates, and phosphates; organic acid salts such as formates, acetates, propionates, and oxalates; of alkali metals such as magnesium, calcium, strontium, and barium; compounds, chlorides, bromides,
Examples include halogen compounds such as iodides, inorganic acid salts such as nitrates, sulfates, perchlorates, and phosphates, and organic acid salts such as formates, acetates, propionates, and oxalates. Among these metal salts, it is preferable to use alkali metal halogen compounds or alkali metal halogen compounds, and in particular alkali metal chlorides or alkali metal chlorides are used in the method of the present invention. It is preferable. Furthermore, as mentioned above, it is preferable to use a basic compound containing an alkali metal as the basic compound, but in this case, it is preferable to carry out the reaction in the coexistence of an alkali metal salt. When a basic compound is used, it is preferable to carry out the reaction in the presence of a sodium salt as a metal salt. Among these, it is particularly preferable to carry out the reaction in the coexistence of sodium hydroxide and sodium chloride. The amount of the basic compound used is usually 0.5 to 1.0 in molar ratio to the phenol. is preferably in the range of 0.7 to 1.2.

The amount of the above-mentioned metal salt used is 0.0% in concentration in the solution in the reaction system.
It can be selected in a wide range from 2 mol/day to saturated solubility, but from an economical point of view, it ranges from 0.5 mol/day to 2.0 mol/day.
Preferably, it is in the range of mol/mol. The reaction of the present invention is usually carried out in an aqueous solution, but if necessary, other water-soluble organic solvents such as alcohols, ketones or A mixture of nitriles can also be used.

It can also be carried out in a solvent such as dimethylsulfoxide, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, hexamethylphosphortriamide, etc., which can dissolve the basic compound and metal salt. In the method of the invention, the reaction is usually 20 to 10
It is carried out at a temperature of 0°C, preferably 40°C, 90qo.

In the method of reacting phenols and formaldehyde when carrying out the method of the present invention, (1) A mixture consisting of phenols, formaldehyde, a basic compound, a metal salt, and, if necessary, a solvent is mixed at the above-mentioned temperature. Method: ■ Continuously supplying formaldehyde to a mixture consisting of phenols, basic compounds, metal salts, and if necessary a solvent, or ■ Method of continuously supplying formaldehyde to a mixture consisting of formaldehyde, a metal salt, and a solvent. Any method can be employed, such as a method of continuously supplying a mixture of phenols, a basic compound, and, if necessary, a solvent to the undercoat. Among these methods, ■
It is preferable to employ the method described above because 3,3,5,5-tetrahydroxymethyl-4,4'-dihydroxydiphenylmethanes can be obtained in high yield. No matter which method is adopted, 3, 3, 5
・5-Tetrahydroxymethyl-4,4-dihydroxydiphenylmethane usually precipitates as its alkali metal salt or alkali metal salt, but when the amount of basic compound used is less than that of phenol, 3.3.
It exists as 5,5-tetrahydroxymethyl-4,4'-dihydroxydiphenylmethanes. After completion of the reaction, the mixture is isolated by concentration or other conventional treatment, and further acid-fractionated to obtain the desired product, 3,3,5,5'-tetrahydroxymethyl-4. 4-dihydroxydiphenylmethanes are obtained. Next, the method of the present invention will be specifically explained using examples.

Example 1 After purging the contents of a separable flask with an internal volume of 1.0 and a condenser, a flywheel, and a dropping funnel with N2 gas, 30% by weight formalin (containing 3.0 moles of formaldehyde) was placed inside the flask. ) and sodium chloride (0.5 mol), and while maintaining the temperature at 40°C, add 94 mol of phenol (1.0 mol), sodium hydroxide (1.0 mol), and 8 mol of water from the dropping funnel.
A mixed solution consisting of 100ml was added dropwise over a period of 10 minutes.

After the dropping was completed, rope worship was continued for 1 hour at that temperature, and then the temperature was further raised to 70 oo and rope worship was continued for 5 hours. After the reaction was completed, a certain amount of the reaction mixture was taken, acetic acid was added thereto to acidify the product, and then the product was subjected to liquid chromatography (G.P.C.
．． ) at the neck. 3, 3, 5, 6 generated by
The amount of -tetrahydroxymethyl-4,4'-dihydroxydiphenylmethane was determined. As a result, the total amount of 3,3,5,5'-tetrahydroxymethyl-4,4'-dihydroxydiphenymethane produced by the reaction was 10
8.8 hours, and the yield based on the phenol charged was 6.
It was 8%. In addition, after cooling the reaction mixture after the completion of the reaction,
After filtration and drying, the sodium salt of 3,3,5,5-tetrahydroxymethyl-4,4'-dihydroxydiphenylmethane was obtained.

By acidifying this with dilute hydrochloric acid, 3, 3, 5, 5-
75.2 hours of tetrahydroxymethyl-4,4-dihydroxydiphenylmethane were isolated. The yield of 3,3',5,5-tetrahydroxymethyl-4,4'-dihydroxydiphenylmethane was 47% based on the phenol used.
It was mol%.

Comparative Example 1 The same procedure as in Example 1 was carried out except that sodium chloride was not used.

As a result, 3.
The production amount of 3,5,5'-tetrahydroxymethyl-4,4'-dihydroxydiphenylmethane was 97.6 evenings (6
The amount of 3,3',5,6-tetrahydroxymethyl-4,4'-dihydroxydiphenylmethane isolated was 40 (25 mole%). Example 2
~11, Comparative Examples 2 to 7 Using the same reaction apparatus as Example 1, the composition of the mixture consisting of formalin and metal salts charged into the flask, the phenol dripped from the dropping funnel,
The reaction was carried out in the same manner as in Example 1, except that the composition of the mixture consisting of the basic compound and water and the reaction conditions were changed as shown in Table 1.

After the reaction was completed, the mixture was post-treated in the same manner as in Example 1. The results are shown in Table 1. Table - Example 12 Using the same equipment as in Example 1, 203 ml of formalin (containing 2.5 mol of formaldehyde) and 30 mol of sodium chloride (containing 0.5 mol) were placed inside the flask, and 2000
While holding the rope, remove the 2.2-screw (
4-Hydoxyphenyl)propane (0.5 mol) and sodium hydroxide (1.0 mol) and water 1
A mixed solution consisting of 0.00 and 0.00% was added dropwise over a period of 20 minutes.

After the dropping was completed, 6-drilling was carried out at the same temperature. After the reaction was completed, the mixture was subjected to post-treatment in the same manner as in Example 1. As a result, the yield of isolated 2,2-bis(3,5-dihydroxymethyl-4-hydroxyphenyl)propane was 90% based on the charged 2,2-bis(4-hydroxyphenyl)propane. Comparative Example 8 The same procedure as in Example 7 was carried out in Example 12 except that sodium chloride was not used.

Claims (1)

[Scope of Claims] 1. At least one basic compound (a) selected from the group consisting of basic compounds containing alkali metals or alkaline earth metals, and the group consisting of alkali metal salts and alkaline earth metal salts. Phenol and bis(4-
3,3',5,5'-tetrahydroxymethyl-4,4'-dihydroxydiphenylmethane, which is characterized by reacting a phenol selected from the group consisting of (hydroxyphenyl)methane with formaldehyde. manufacturing method. 2. The method according to claim 1, wherein an alkali metal halogen compound or an alkaline earth metal halogen compound is used as the metal salt (b). 3 The basic compound (a) is used in a molar ratio of 0.7 to 1.2 to the phenols, and the metal salt (b) is used in a concentration of 0.5 to 1 in the solution in the reaction system.
．． The method according to claim 1, wherein the amount is used in the range of 2 mol/l. 4. The method according to claim 1, wherein the reaction is carried out in an aqueous solvent. 5. The method according to claim 1, wherein the reaction is carried out at a temperature of 40 to 90°C. 6. The method according to claim 1, wherein in the method of reacting phenols with formaldehyde, formaldehyde is used in a molar ratio of 2 to 3.5 to the phenols. 7 In a method of reacting phenols and formaldehyde, a mixture consisting of phenols, a basic compound, and an optional solvent is continuously supplied to a mixture consisting of formaldehyde, a metal salt, and an optional solvent under stirring. The method according to claim 1, wherein the reaction is carried out while the reaction is being carried out.